CN105873687A

CN105873687A - Adhesion promoter for solventborne primer surfacers

Info

Publication number: CN105873687A
Application number: CN201480068157.6A
Authority: CN
Inventors: A·安德森; C·科尔顿; M·尼迈尔; F·福灵; S·海森奈尔; N·弗莱塔格; S·博世-普鲁伊斯
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2013-12-17
Filing date: 2014-12-17
Publication date: 2016-08-17
Anticipated expiration: 2034-12-17
Also published as: WO2015091662A1; US9932483B2; US20160312036A1; EP2886208A1; RU2016129050A; CA2931394A1; JP2017507197A; KR20160099625A; CN105873687B; EP3083081B1; EP3083081A1

Abstract

The present invention relates to a solventborne primer surfacer which comprises at least one additive preparable by reacting at least one alpha,omega-hydroxy-functionalized oligoester which possesses an OH number of 30 to 60 mg KOH/g, a theoretical carbon- carbon double bond content of 1 to 2.5 mmol/g, a number-average molecular weight of 1000 to 3000 g/mol, and a weight-average molecular weight of 2800 to 10 000 g/mol, and at least one alkoxysilane which possesses an OH-reactive functional group, the sum of the weight percentage fractions of all additives of the invention being 0.5 to 10 wt%, based on the total amount of the solventborne primer surfacer.The present invention further relates to a process for producing multicoat paint systems, and to multicoat paint systems producible by means of said process. The invention further relates to the use of the additive identified above in solventborne primer surfacers for improving adhesion.

Description

Solvent bottom paint surfacer adhesion promoter

The present invention relates to a kind of solvent bottom paint surfacer.On base material, multicoat paint body is produced further to one Corresponding multicoat paint systems in the method for system and base material.Finally, the present invention relates to additive of the present invention at the bottom of solvent-borne type Paint surfacer improves the purposes of attachment.

Prior art

Finish on light economic serviceable vehicle is restricted by being strict with.In typical system, scribbling Priming paint surfacer coating and finish paint has been applied on the metal base of electrocoating paint system.Finish paint generally has priming coat concurrently with saturating The function that bright coating is mutual.Therefore, finish paint such as comprises pigment and is the most substantially responsible for the integral colouring outward appearance of paint systems.This Outward, it also has the Typical mass feature of clear coat, such as corresponding resistance to marring.Both priming paint surfacer and finish paint are usual It is solvent-based system.The covering with paint of light economic serviceable vehicle is frequently not automated procedures.In other words, described coating hands is executed It is coated with, the most such as by spray application.Mainly two-component paints system is used in these situations, it is allowed to solid at mild temperature Change.In gained paint finish, attachment between subject matter or priming paint surfacer coating and finish paint and also priming paint two Attachment between road slurry and base material.

Similar Problems also appears in automobile recoating.Automobile recoat in, must reproduce after accident japanning result or Person must remedy covering with paint error.Automotive paint systems such as can pass through sand milling damaged location and apply priming paint, priming paint two road subsequently Slurry, priming coat and clear coat and recoat.Paint systems the most used is different from automotive OEM covering with paint.Its key is former Cause is that automobile recoating must be carried out on the automobile assembling completely and installing.But, the automobile assembling completely and installing may be sudden and violent It is exposed to only 60 DEG C until the temperature of the highest 100 DEG C.Therefore, main use allows the two-component paints solidified at these tem-peratures System.Here an also problem is between the attachment between priming paint surfacer coating and priming coat and priming paint surfacer and priming paint Attachment.

Purpose

Therefore, the invention aims to improve the attachment between priming paint surfacer coating and adjacent coating thereof.This priming paint Surfacer to be suitable for covering with paint, lacquer, colour wash, etc. in both light economic serviceable vehicle and automobile recoating.Covering with paint, lacquer, colour wash, etc. light economic serviceable vehicle In the case of, it is therefore an objective to attachment between priming paint surfacer coating to be improved and finish paint and also between priming paint surfacer and base material Attachment.In the case of automobile recoats, it is of concern that attachment between priming paint surfacer coating to be improved and priming coat and Also has the attachment between priming paint surfacer and priming paint.

The technology of the present invention solution

This purpose shockingly solves by a kind of solvent bottom paint surfacer, and it comprises at least one can be as follows by making Component reaction and the additive prepared:

A () at least one OH value is 30-160mg KOH/g, theoretical carbon-to-carbon double bond content is 1-2.5mmol/g, number is divided equally Son amount is the α of 2800-10000g/mol for 1000-3000g/mol and weight average molecular weight, ω-hydroxy-functional oligoester, and

The alkoxy silane of (b) at least one structure formula (II):

A-R-Si(R’)_x(OR”)_3-x

Wherein

A is OH reactive functional group,

R is to have the aliphatic group of 2-12 carbon atom, have the alicyclic group of 3-12 carbon atom, have 6-12 The aromatic group of carbon atom or there is the araliphatic groups of 7-18 carbon atom,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2,

Condition is α, in all OH groups of ω-hydroxy-functional oligoester at least 90mol% with OH reactivity official Can react by group A,

And the weight percent ratio sum of the most all additives of the present invention is based on solvent bottom paint surfacer total Amount is 0.5-10 weight %.

At least 95mol%, more preferably at least 97mol% in all OH groups of preferably α, ω-hydroxy-functional oligoester, Especially at least 99mol%, and also 100mol% with OH reactive functional group A is reacted.With alkoxy silane (II) the OH group amount of the α, ω of OH reactive functional group A reaction-hydroxy-functional oligoester such as can be by measuring The amount of still unreacted OH reactive functional group A of alkoxy silane (II) and indirect determination.

The explanation of α, ω-hydroxy-functional oligoester

Term α, ω-hydroxy-functional oligoester represents that the opposite end being represented by α and ω respectively is individually present hydroxyl Oligoester.This means that such oligoester is blocked by the most just monomeric unit with a hydroxyl at two ends. When oligoester is branched, α and ω relates to the end of the longest polymer chain in monomer.This length is fixed by the number of monomers mixed Justice.α, ω-hydroxy-functional oligoester is not to have other hydroxyls.α the most used according to the present invention, ω-hydroxyl Base functionalized oligomeric ester has just 2 hydroxyls, one α position and one in ω position.The most used according to the present invention α, ω-hydroxy-functional oligoester have just 2 hydroxyls one α position and one in ω position and also for linear.

The OH value that α used according to the present invention, ω-hydroxy-functional oligoester has is preferably 40-160mg KOH/g, More preferably 70-150mg KOH/g.OH value can be measured as following according to DIN 53240-2 (date: in November, 2007).Pass through OH radical reaction is made with excessive acetic acid acid anhydride acetylation.Excessive acetic acid acid anhydride forms acetic acid by adding water-splitting and uses subsequently The whole acetic acid of KOH ethanol solution back titration.OH value represents the KOH amount in terms of mg, and it is equal to combination in acetylation 1g material Acetic acid amount.

α used according to the present invention, ω-hydroxy-functional oligoester has preferably 0-10mg KOH/g further, more Preferably 0-5mg KOH/g, the acid number of highly preferred 0-3mg KOH/g.Acid number is according to the DIN EN ISO 2114 (date: 2002 June) measure.In this mensuration, dissociate present in standardized KOH solution titration sample in the presence of colored indicator Acid.Acid number is corresponding to the quality of potassium hydroxide needed for neutralization 1g α, ω-hydroxy-functional oligoester under the described conditions, with mg Meter.

α, ω-hydroxy-functional oligoester has 1000-2000g/mol, more preferably 1200-1800g/mol further Preferred number average molecular weight and the weight average molecular weight of the most preferred 3000-8000g/mol, more preferably 3000-6000g/mol.Number All use polystyrene standards according to DIN with weight average molecular weight by the gel permeation chromatography using oxolane as eluant 55672-1 (date: in August, 2007) measures.Column material is made up of styrene diethylene benzene copoly mer.

The present invention is necessary that, and α, ω-hydroxy-functional oligoester has 1-2.5mmol/g, preferably 1.5-2mmol/g, The theoretical carbon-to-carbon double bond content of more preferably 1.6-1.9mmol/g.Theoretical carbon-to-carbon double bond content relates to carbon-to-carbon double bond with unit The amount of the material of mmol meter, based on α, ω-hydroxy-functional oligoester quality in terms of unit of gram.Formula shown in below claims Theoretical carbon-to-carbon double bond content for double bond content is calculated as follows:

The amount (double bond) of double bond content=material/quality (oligoester)

Here statement " amount (double bond) of material " relates to amount and the statement of carbon-to-carbon double bond material in terms of unit mmol " quality (oligoester) " relates to α, ω-hydroxy-functional oligoester quality in terms of unit of gram.

The quality of α, ω-hydroxy-functional oligoester is that the monomer summation in it is prepared deducts the water formed wherein Quality, it is assumed that all anhydride groups and hydroxy-acid group convert completely.The amount of the material of carbon-to-carbon double bond is by unsaturated monomer used The amount of material be given.Such as when only using single unsaturated monomer such as maleic anhydride, the amount of the material of carbon-to-carbon double bond is equal to institute Amount with the material of unsaturated monomer.Such as when using two unsaturated monomers, this monomer introducing α, ω-hydroxy-functional is low The amount of the material of the carbon-to-carbon double bond in polyester doubles the amount of the material of corresponding two unsaturated monomers used.

α, ω-hydroxy-functional oligoester such as can be prepared by the reaction of polycarboxylic acid with polyhydric alcohol.It is preferably by dicarboxyl Prepared by the reaction of acid and also its anhydride and glycol, triol and mono hydroxy functional's compound.Glycol is preferably used.

When preparing α, ω-hydroxy-functional oligoester with dicarboxylic acids, its anhydride can also be used in principle.Therefore, exist Hereinafter, term dicarboxylic acids should be interpreted that and includes corresponding anhydride equally.Decision is with dicarboxylic acids or to use described with anhydride Compound is a part for those of ordinary skill in the art's general knowledge.

Dicarboxylic acids

Dicarboxylic acids can be aromatics or aliphatic compounds used according to the present invention.Aliphatic compounds are free from any aromatics The compound of group such as phenyl.Aromatic compounds includes all including that at least one aromatic group is as optionally taken for the present invention Those compounds of the phenyl in generation.The example of aromatic compounds such as includes the structure of phthalic acid known to the skilled artisan Isomer and also include terephthalic anhydride.

Preferred aliphatic series dicarboxylic acids.Particularly preferably aliphatic dicarboxylic acid is saturated or list-or polyunsaturated.The most saturated Or single-or polyunsaturated linear aliphatic dicarboxylic acids.In addition to these, it is also possible to use alicyclic dicarboxylic acid.

Furthermore it is preferred that use at least one radical of saturated aliphatic dicarboxylic acids and at least one list-or multi-section radical of saturated aliphatic dicarboxylic acids.

Particularly preferably use at least one saturated linear aliphatic dicarboxylic acid and at least one list-or many unsaturated linear aliphatic Dicarboxylic acids.Particularly preferably use just a kind of radical of saturated aliphatic dicarboxylic acids and just a kind of list-or many unsaturated aliphatics dicarboxylic acids.Non- The most particularly preferably a kind of saturated linear aliphatic dicarboxylic acid of use and just a kind of list-or many unsaturated linear aliphatic dicarboxyls Acid.

Radical of saturated aliphatic dicarboxylic acids with single-and/or the mol ratio of many unsaturated aliphatics dicarboxylic acids be preferably 0.5:1.5-1.5: 0.5, particularly preferred 0.75:1.25-1.25:0.75, highly preferred 0.9:1.1-1.1:0.9.Described ratio relates to wherein using More than one saturated dicarboxylic acid and/or more than one unsaturated dicarboxylic and wherein use just a kind of saturated dicarboxylic acid and just Good a kind of unsaturated dicarboxylic both of these case.

Radical of saturated aliphatic dicarboxylic acids used preferably has 4-18, more preferably 6-14, highly preferred 6-10 carbon atom Those.Particularly preferably these are linear saturated aliphatic dicarboxylic acids.

Single unsaturated aliphatic dicarboxylic acids used preferably has 4-10, and more preferably 4-8, highly preferred 4-6 carbon is former Those of son.Particularly preferably these are corresponding unsaturated linear aliphatic dicarboxylic acids.

Many unsaturated aliphatics dicarboxylic acids used preferably has 6-18, more preferably 8-16, highly preferred 10-14 carbon Those of atom.Particularly preferably these are corresponding how unsaturated linear aliphatic dicarboxylic acids.

Radical of saturated aliphatic dicarboxylic acids for example, chain docosandioic acid.It is preferably used containing 4-18, more preferably 6-14, very preferably The saturated chain docosandioic acid of 6-10 carbon atom.Particularly preferably these are containing 4-18, more preferably 6-14, highly preferred 6-10 The saturated linear alkane diacid of individual carbon atom.Suitably chain docosandioic acid for example, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., pungent Diacid, Azelaic Acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid and hexadecandioic acid (hexadecane diacid), with And also have its anhydride, if if the latter exists.

The single unsaturated aliphatic dicarboxylic acids that can use is containing 4-10, more preferably 4-8, highly preferred 4-6 carbon The chain enedioic acid of atom.Preferably these are corresponding single unsaturated linear chain enedioic acid.Suitable single unsaturated linear chain enedioic acid Example be maleic acid.

Glycol

The glycol being preferably used can be aromatics or aliphatic compounds.Preferred aliphatic series glycol.Particularly preferably they are linear Or cycloaliphatic diol.These glycol can be saturated or list-or polyunsaturated.Preferably they are saturated linear aliphatic diol Or saturated cyclic aliphatic diol.

It is, for example possible to use have 4-18, more preferably 6-14, the radical of saturated aliphatic two of highly preferred 6-10 carbon atom Alcohol.Preferably these are corresponding saturated linear aliphatic diol or saturated cyclic aliphatic diol.

Saturated alkanediol or saturated cycloalkanes glycol are preferably used.A rear glycol can be mononaphthene glycol, dicyclo alkane two Alcohol or three cycloalkanes glycol.Such as can use and there is 4-18, more preferably 6-14, highly preferred 6-10 carbon atom saturated Alkanediol.Preferably these are corresponding saturated linear alkanediol.Suitable saturated alkanediol for example, 1,4-butanediol And 1,6-HD.

Preferably can also use and there is 6-18, more preferably 6-14, the saturated cyclic of highly preferred 6-10 carbon atom Aliphatic diol.

Preferably can use and there is 6-18, more preferably 6-14, the saturated cycloalkanes two of highly preferred 6-10 carbon atom Alcohol.The saturated cycloalkanes glycol particularly preferably used is three ring decanediols, cyclohexane dimethanol and tetramethyl-ring butanediol.

α, ω-hydroxy-functional oligoester uses excess diol to prepare.The mol ratio of dicarboxylic acids and glycol is the most for example, N:(n+1.1)-n:(n+2), preferably n:(n+1.2)-n:(n+1.8), more preferably n:(n+1.3) and-n:(n+1.6), very preferably N:(n+1.3)-n:(n+1.5), wherein n represents the amount of material of dicarboxylic acids.

α, ω-hydroxy-functional oligoester is prepared in the way of known to the skilled artisan.In order to obtain reactant used Quantitative yield, it is necessary to balance chemically removes the water formed in course of reaction.This is mainly by using water separator to carry out. Therefore, α, ω-hydroxy-functional oligoester is polycondensation product.Therefore, α, ω-hydroxy-functional oligoester composition has different chain The mixture of long corresponding oligoester.

In a preferred embodiment of α used according to the present invention, ω-hydroxy-functional oligoester, it uses extremely Few a kind of saturated linear aliphatic dicarboxylic acid, at least one single unsaturated linear aliphatic dicarboxylic acids and at least one radical of saturated aliphatic glycol Preparation.Saturated linear aliphatic dicarboxylic acid used preferably has 4-18, more preferably 6-14, highly preferred 6-10 carbon atom Linear chain docosandioic acid.Single unsaturated linear dicarboxylic acid preferably has 4-10, more preferably 4-8, highly preferred 4-6 carbon The single unsaturated linear chain enedioic acid of atom.Radical of saturated aliphatic glycol preferably includes have 4-18, more preferably 6-14, the most excellent Select the saturated linear alkanediol of 6-10 carbon atom or also, it is preferred that include that there is 6-18, more preferably 6-14, very The saturated cycloalkanes glycol of preferably 6-10 carbon atom.

Additionally, certainly triol and mono hydroxy functional can also be used to close when preparing α, ω-hydroxy-functional oligoester Thing.It is, for example possible to use aliphatic triol and also aliphatic monohydroxy groups functional compound.These are preferably corresponding aliphatic hydrocarbonylation Compound.The triol example that can be given is trimethylolpropane.As mono hydroxy functional's compound, such as, can use dodecane Alcohol.

In a further preferred embodiment, α, ω-hydroxy-functional oligoester has a having structure formula (I):

Wherein

Group R₁It is independently selected from linear or cyclic alkylidene,

Group R₂It is independently selected from the ratio of alkylidene or alkylene group, the most specifically chosen alkylidene and alkylene group Example so that the α of structure formula (I), ω-hydroxy-functional oligoester has the theoretical carbon-to-carbon double bond content of 1-2.5mmol/g,

Select exponent m so that the number-average molecular weight of the α of structure formula (I), ω-hydroxy-functional oligoester is 1000- 3000g/mol。

Exponent m in structure formula (I) is the integer more than 0.

Exponent m should be selected so that the number-average molecular weight of the α of structure formula (I), ω-hydroxy-functional oligoester is 1000- This requirement of 3000g/mol will be explained below.Assuming that all group R₁For hexa-methylene and whole m group R₂Middle half It is respectively tetramethylene and second half is respectively the group of formula-CH=CH-.If such as number-average molecular weight is 1500g/mol, then m Average out to 6-7.

The number-average molecular weight of the α of structure formula (I), ω-hydroxy-functional oligoester is preferably 1000-2000g/mol, more excellent Select 1200-1800g/mol.

The weight average molecular weight of the α of structure formula (I), ω-hydroxy-functional oligoester is preferably 3000-8000g/mol, more excellent Select 3000-6000g/mol.

The OH value that the α of structure formula (I), ω-hydroxy-functional oligoester has is preferably 40-160mg KOH/g, more preferably 70-150mg KOH/g。

The theoretical carbon-to-carbon double bond content that the α of structure formula (I), ω-hydroxy-functional oligoester has is preferably 1.5- 2mmol/g, more preferably 1.6-1.9mmol/g.

The acid number that the α of structure formula (I), ω-hydroxy-functional oligoester has is preferably 0-10mg KOH/g, more preferably 0- 5mg KOH/g, highly preferred 0-3mg KOH/g.Theoretically, the acid number of the α of structure formula (I), ω-hydroxy-functional oligoester For 0mg KOH/g.If described oligoester is by corresponding glycol and also has corresponding dicarboxylic acids and/or its anhydride to prepare, the most former Then go up and can there is the hydroxy-acid group not yet reacted with corresponding glycol.Now, the acid number that products therefrom mixture has > 0mg KOH/g.According to above scope described in acid number, preferably gained reactant mixture being had the fewest hydroxy-acid group.

Independently of each other, group R¹Selected from linear or cyclic alkylidene.If more than one group R₁It is present in structure formula (I) α, ω-hydroxy-functional oligoester in, then their arrangement is statistically.In the case of linear alkylene, it is preferred Containing 4-18, more preferably 6-14, highly preferred 6-10 carbon atom.Very particularly preferably this is hexa-methylene.Ring-type In the case of alkylidene, it preferably comprises 6-18, more preferably 6-14, highly preferred 6-10 carbon atom.The most excellent Selecting this is tricyclodecyl.

Independently of each other, group R₂Selected from alkylidene or alkylene group, the most specifically chosen alkylidene and alkylene group Ratio so that the α of structure formula (I), ω-hydroxy-functional oligoester has 1-2.5mmol/g, preferably 1.5-2mmol/g, non- The theoretical carbon-to-carbon double bond content of Chang Youxuan 1.6-1.9mmol/g.Variety classes group R₂The α of structure formula (I), ω-hydroxyl official Can change the arrangement in oligoester is statistically.

R₂It is preferably linear alkylene or linear alkylene group.Also, it is preferred that the mol ratio between alkylidene and alkylene group For 0.5:1.5-1.5:0.5, particularly preferred 0.75:1.25-1.25:0.75, highly preferred 0.9:1.1-1.1:0.9.

If R₂For linear alkylene, then it preferably comprises 2-16, more preferably 4-12, highly preferred 4-8 carbon atom. Its for example, tetramethylene.

Additionally, R₂It can be linear alkylene group.This group preferably preferably comprises 2-8, more preferably 2-6, very The single unsaturated linear alkylene group of preferably 2-4 carbon atom.Very particularly preferably it is the alkylene group of structure-CH=CH-.

The explanation of the alkoxy silane of structure formula (II)

Aliphatic group R is such as organic group without aromatic group such as phenyl.Aliphatic group R can have 2-12 Carbon atom.Alicyclic group R is such as organic group without aromatic group such as phenyl.Alicyclic group R can have 3- 12 carbon atoms, such as in the case of cyclopropyl or cyclohexyl.Aromatic group R is such as by aromatic group such as Asia The organic group that phenyl is constituted.Aromatic group R can have 6-12 carbon atom.Araliphatic groups R is for not only having aromatic group Roll into a ball and there is the organic group of aliphatic group.Araliphatic groups R can have 7-18 carbon atom.As aliphatic group R's Group R can also contain hetero atom such as oxygen, nitrogen or sulfur in addition to carbon and hydrogen.Additionally, the most equally there is it His functional group, such as ester group or urethane group.Additionally, group R equally contains alkene or alkyne group.It is equally Polyunsaturated and/or equally contain more than one alkyne group.R more preferably has 2-12 carbon atom or 2-10 is individual Carbon atom, highly preferred 2-8 carbon atom, the aliphatic group of especially 2-6 carbon atom.For those of skill in the art clear Be group R be divalent group.

Group R ' is preferably C₂-C₁₀Alkylidene, more preferably C₂-C₈Alkylidene, highly preferred C₃-C₆Alkylidene.

OH reactive functional group A is preferably isocyanate groups or epoxide group.More preferably isocyanate groups.

The alkoxy silane of general structural Formula (II.1) be preferably used:

OCN-R₁-Si(R’)_x(OR”)_3-x

Wherein

R₁For C₂-C₁₂Alkylidene, C₂-C₁₂Alkylene group or many unsaturated C₄-C₁₂Alkylidene,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2.

Preferably R₁For C₂-C₁₂Alkylidene or even C₂-C₁₀Alkylidene.More preferably it is C₂-C₈Alkylidene, highly preferred C₂- C₆Alkylidene or C₃Alkylidene.About group R ', it is referred to preferably, more preferably and very preferably feature described above.Additionally, x It is preferably 0 or 1, highly preferred x=0.

Alkoxy silane again preferably with general structural Formula (II.2):

Wherein

R₂For C₂-C₁₀Alkylidene, C₂-C₁₀Alkylene group or many unsaturated C₄-C₁₀Alkylidene,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2.

Preferably R₂For C₂-C₁₀Alkylidene or even C₂-C₈Alkylidene.More preferably it is C₂-C₆Alkylidene, highly preferred C₂- C₄Alkylidene or C₃Alkylidene.About group R ', it is referred to preferably, more preferably and very preferably feature described above.Additionally, x It is preferably 0 or 1, highly preferred x=0.

Alkoxy silane again preferably with general structural Formula (II.3):

Wherein

R₃For C₂-C₁₂Alkylidene, C₂-C₁₂Alkylene group or many unsaturated C₄-C₁₂Alkylidene,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2.

Preferably R₃For C₂-C₁₂Alkylidene or even C₂-C₁₀Alkylidene.More preferably it is C₂-C₈Alkylidene, highly preferred C₂- C₆Alkylidene or C₃Alkylidene.About group R ', it is referred to preferably, more preferably and very preferably feature described above.Additionally, x It is preferably 0 or 1, highly preferred x=0.The preparation of additive of the present invention

Additive of the present invention such as by making at least one α, ω-hydroxy-functional oligoester and at least one structural formula (II) alkoxy silane reacts and prepares.This reaction is carried out in organic solvent.Suitably solvent be those of skill in the art All solvents of the most active H atom known.The example of suitable solvent is esters such as butyl acetate or Petroleum.This reaction can Optionally to carry out in the presence of at least one water scavenger is such as triethyl orthoformate.Preferably it is firstly introduced into the alcoxyl of structure formula (II) Base silane, then drips α, ω-hydroxy-functional oligoester.When A is isocyanate groups, reaction solution remains Carbimide. The amount of ester group such as can be measured according to DIN EN ISO 11909 (date: in May, 2007) by titrimetry.When A is ring During oxide groups, in reaction solution, the amount of residue ring oxide groups can be by titrimetry such as according to DIN EN ISO 3001 measure (date: in November, 1999).

In a particularly preferred embodiment of additive of the present invention, it is by making the α of at least one structure formula (I), The alkoxy silane of ω-hydroxy-functional oligoester and at least one structural formula (II.1) reacts and prepares.

Other particularly preferred embodiments of additive of the present invention are as shown below:

A) in a particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Polyester has the number-average molecular weight of 1200-1800g/mol.

B) in another particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Polyester has the weight average molecular weight of 3000-6000g/mol.

C) in another particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Polyester has the OH value of 70-150mg KOH/g.

D) in another particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Polyester has the theoretical carbon-to-carbon double bond content of 1.5-2mmol/g.

E) in another particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Group R in polyester₁Selected from the linear alkylene with 6-10 carbon atom.

F) in another particularly preferred embodiment of additive of the present invention, the α of structure formula (I), ω-hydroxy-functional is low Group R in polyester₂Selected from there is the linear alkylene of 4-8 carbon atom or there is the linear alkylene group of 2-4 carbon atom.

G) at additive of the present invention or the α of structure formula (I), another of ω-hydroxy-functional oligoester is particularly preferably implemented In scheme, the mol ratio between linear alkylene and linear alkylene group is 0.9:1.1-1.1:0.9.

H) in another particularly preferred embodiment of additive of the present invention, base in the alkoxy silane of structural formula (II.1) Group R₁For C₂-C₆Alkylidene.

I) in another particularly preferred embodiment of additive of the present invention, x in the alkoxy silane of structural formula (II.1) It is 0.

J) in another particularly preferred embodiment of additive of the present invention, owning of α, ω-hydroxy-functional oligoester In OH group, at least 99mol% reacts with OH reactive functional group A of alkoxy silane of the present invention.

In the particularly preferred embodiment of α of the present invention, ω-hydroxy-functional oligoester, combination realize at a)-j) under institute Show all features.

The explanation of solvent bottom paint surfacer

The present invention is necessary that, and solvent bottom paint surfacer comprises at least one additive of the present invention.All present invention add The weight percent ratio sum total amount based on solvent bottom paint surfacer adding agent is 0.5-10 weight %.All present invention add The weight percent ratio sum adding agent is preferably 1-9 weight %, more preferably 1-8 weight %, highly preferred 1.5-7.5 weight % Or even 1.5-6.5 weight %, gross weight based on priming paint surfacer in each case.

Improvement is not the most adhered to less than the lower limit of 0.5 weight %.Shortcoming then occurs, such as gained higher than the upper limit of 10 weight % Coating yellowing.

In solvent bottom paint surfacer of the present invention, the weight percent ratio sum of additive of the present invention is based on solvent-borne type The total amount of priming paint surfacer is 0.5-10 weight %.When using the preferred embodiment of additive of the present invention, the institute of additive The weight percent ratio sum total amount based on solvent bottom paint surfacer having preferred embodiment is preferably again 0.5-10 Weight %.Particularly preferably priming paint surfacer of the present invention only comprises the preferred embodiment of additive as corresponding additive.

In a preferred embodiment of solvent bottom paint surfacer of the present invention, the percetage by weight of additive of the present invention Ratio sum total amount based on solvent bottom paint surfacer is 1-9 weight %.When the side of being preferable to carry out using additive of the present invention During case, the weight percent ratio sum total amount based on solvent bottom paint surfacer of all preferred embodiments of additive is same Sample is preferably 1-9 weight %.Particularly preferably priming paint surfacer of the present invention only comprises the preferred embodiment of additive as correspondence Additive.

In a particularly preferred embodiment of solvent bottom paint surfacer of the present invention, the weight hundred of additive of the present invention Fraction scale sum total amount based on solvent bottom paint surfacer is 1-8 weight %.When using the preferred real of additive of the present invention When executing scheme, the weight percent ratio sum of all preferred embodiments of additive is based on solvent bottom paint surfacer total Amount preferably again 1-8 weight %.The particularly preferably priming paint surfacer of the present invention only comprises the preferred embodiment work of additive For corresponding additive.

In a particularly preferred embodiment of solvent bottom paint surfacer of the present invention, the weight hundred of additive of the present invention Fraction scale sum total amount based on solvent bottom paint surfacer is 1.5-7.5 weight %.When using the excellent of additive of the present invention When selecting embodiment, the weight percent ratio sum of all preferred embodiments of additive is based on solvent bottom paint surfacer Total amount be preferably again 1.5-7.5 weight %.The particularly preferably priming paint surfacer of the present invention only comprises the preferred real of additive Scheme of executing is as corresponding additive.

In the same particularly preferably embodiment of the solvent bottom paint surfacer of the present invention, the weight of additive of the present invention Percentage sum total amount based on solvent bottom paint surfacer is 1.5-6.5 weight %.When using additive of the present invention During preferred embodiment, the weight percent ratio sum of all preferred embodiments of additive is based on solvent bottom paint two road The total amount of slurry is preferably again 1.5-6.5 weight %.The particularly preferably priming paint surfacer of the present invention only comprises the preferred of additive Embodiment is as corresponding additive.

The example of the preferred embodiment of additive of the present invention is explanation with regard to additive of the present invention thus Those described.

The solids content of priming paint surfacer can be by by about 2g samples weighing to the aluminum dish being dried in advance and dry Case is dried 60 minutes in 125 DEG C, then cools down in exsiccator and be re-weighed subsequently and measure.Total relative to specimen in use Amount, residue corresponds to solid fraction.Solids content (1-2g is determined according to DIN EN ISO 3251 (date: in June, 2008) 1 hour is continued) at 125 DEG C.

The solvent bottom paint surfacer known to those of skill in the art can be used.It is organic that priming paint surfacer comprises at least one Polymer is as base material.Polyester resin that these organic polymers are the most known to the skilled artisan and/or polyacrylate With polymethacrylate resin (the most poly-(methyl) acrylate).Described organic polymer preferably further wraps Containing the different functional groups for chemical crosslinking, preferably hydroxyl.The polyester resin that preferably comprise hydroxyl is preferably used as base material And/or poly-(methyl) acrylate.Organic polymer and the resin of these kinds are such as described in- Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, the In 73-74 page.Polyester produces the most pliable and the toughest priming paint surfacer.In view of its faster physical dryness and they finally allow More in early days the fact that of processing, the most poly-(methyl) acrylate.Further, it is also possible to use epoxy resin.These resins Such as it is described in-Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, in 196-197.A kind of epoxy resin being preferably used thus is Epikote 1001.Polyisocyanate adduct can be used as cross-linking agent.In view of its low viscosity and more preferable weatherability, polyisocyanate used Cyanate adduct is aliphatic series and also alicyclic polyisocyanates adduct.These are be also used for that automotive OEM covers with paint, lacquer, colour wash, etc. double Product in component transparent coating.Polyisocyanate adduct used is usually the oligomer of diisocyanate.Polyisocyanates The basis of adduct is such as by hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), diphenylmethyl Alkane diisocyanate (MDI) and tetramethylxylylene diisocyanate (TMXDI) are formed.But, additionally can use All all conventional diisocyanate known to the skilled artisan.Oligomeric method is to be formed different adduct: urethane, urea Carbamate, biuret, diazacyclo diacetyl and preferred isocyanuric acid ester.In view of its viscosity, particularly preferably use six The isocyanurate trimer of methylene diisocyanate.

All film-forming components, especially hydroxyl-functional polyester's resin and/or poly-(methyl) acrylate and conduct The ratio of the polyisocyanate adduct of cross-linking agent is advantageously 10-90 weight %, preferably 15-60 weight %, more preferably 20-50 Weight %, in each case total amount based on solvent bottom paint surfacer.Any resin separately considered as base material and The ratio also having cross-linking agent is beneficially based on the total amount of solvent bottom paint surfacer not less than 3 weight %.

Typically require catalytic crosslinking reaction.To this end, the most always use organic tin salt.For the purpose of the present invention, it is preferably used Dibutyl tin laurate, because its longer chain acidic group gives it with the extra high compatibility of base material and gives it and film subsequently The extra high compatibility of matrix.

The coloring of priming paint surfacer is mainly made up of titanium dioxide and/or iron oxide pigment and carbon black.It is suitable to additionally, there are Filler.The filler that can use can be used for the conventional fillers in coatings industry.Filler is such as described in- Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, the In 250-252 page.Additionally, generally use corrosion inhibitor, such as silicate, orthophosphate and Quadrafos.Only to special circumstances The priming paint surfacer of preparation coloring, it supports the color being planned finish paint coatings.Priming paint surfacer is generally of various ash Tone, this is produced by the ratio of pigment grade carbon black and iron oxides (being in most cases yellow iron oxide).

The priming paint surfacer of the present invention further includes machine solvent.The example of those that can exist include aliphatic series and/ Or aromatic hydrocarbons such as toluene, dimethylbenzene, solvent naphtha, Solvesso 100, Shellsol A, ketone, such as acetone, methyl second Base ketone or methyl amyl ketone, esters, such as ethyl acetate, butyl acetate, acetic acid methoxyl group propyl ester, butyl glycol acetate, second Acid pentyl ester or ethoxyl ethyl propionate, ethers, such as butyl glycol and dipropylene glycol methyl ether, alcohols, such as ethyl hexanol, fourth oxygen Base propanol, isopropanol or butyldiglycol, or the mixture of above-mentioned solvent.

Additionally, priming paint surfacer is solvent type.Term " solvent-borne type " is understood to refer to below only by organic solvent Water is not had as solvent.More specifically, the water content of solvent bottom paint surfacer of the present invention should be not more than 5 weight %, especially It is not more than 2 weight %, in each case total amount based on solvent bottom paint surfacer of the present invention.

Priming paint surfacer can comprise at least one conventional coating additive further.Such coating additive is such as but not It is exclusively:

-defoamer,

-polymerization inhibitor,

-slip additive,

-wetting agent such as siloxanes, fluorochemical, dicarboxylic acid monoester,

-flow control agent,

-rheology control agent,

-dispersant,

-corrosion inhibitor, and/or

-fire retardant.

The explanation of the inventive method

The invention further relates to a kind of method producing multicoat paint systems on base material, including:

(A) the priming paint surfacer of the present invention is applied,

(B) another coating material is applied.

The most with regard to solvent bottom paint surfacer of the present invention discuss all special characteristics equally to described side of the present invention Method is preferred.

In a preferred embodiment of the inventive method,

I. the priming paint surfacer thin film obtained in step (A) it is dried,

Ii. the coating material in step (B) is topcoat material, and

Iii. combination curing is dried priming paint surfacer thin film and the finish paint thin film obtained in step (B).

Present invention is equally related to a kind of multicoat paint that can produce according to this preferred embodiment of the inventive method System.The most with regard to solvent bottom paint surfacer of the present invention and also the inventive method this preferred embodiment discuss All special characteristics are preferred to this multicoat paint systems equally.

The dry discharge relating to solvent for i. section.Film/coating is each described by this contingent condition subsequently Below.Solidification for iii. section refers to heat cure.For the purpose of the present invention, term " heat cure " represents that the heat of film is drawn Send out crosslinking, in parent coating material, wherein use separate cross-linking agent or self-crosslinking base material.Cross-linking agent comprises to be deposited in base material The complementary reactive functional group of reactive functional group.This is generally referred to as outside friendship by those skilled in the art Connection.When complementary interaction functional group or self-reactive functional group, i.e. group with identical type radical reaction has been deposited When being in base material molecule, the base material existed is self-crosslinking.Film/coating is each retouched by heat cure contingent condition subsequently It is set forth in hereinafter.

The method is preferred in the covering with paint of light economic serviceable vehicle.Suitably base material the most especially metal base. Metal base is all that known to those of skill in the art, such as aluminum, ferrum, zinc and magnesium, and also has its alloy.Particularly preferably aluminum Or steel substrate.

Depend on material, it is also possible to provide electrodeposited coating to metal base, such as in the case of steel.If Use aluminium base, electrodeposited coating is not the most provided, but wore away before applying priming paint surfacer.Except metal base Outward, it is also possible to apply all conventional thermoplastic known to the skilled artisan or thermosetting polymer base material.

Finish paint

Solvent-borne type topcoat material known to the skilled artisan can be used.Topcoat material comprises at least one organic polymer Thing is as base material.Polyester resin that these organic polymers are the most known to the skilled artisan and/or polyacrylate and poly- Methacrylate resin (the most poly-(methyl) acrylate).Described organic polymer as base material preferably enters One step comprises the different functional groups for chemical crosslinking, preferably hydroxyl.Do in view of its much better initiateing compared with polyester Dry speed, is preferably used poly-(methyl) acrylate.Particularly preferably use shrink with branched satisfied fatty acid sweet Poly-(methyl) acrylate that grease is modified.This improves its ability accommodating pigment.Cross-linking agent used is low viscous Aliphatic polyisocyanate adduct, the latter's explanation with regard to the solvent bottom paint surfacer of the present invention was discussed.Where like Very particularly preferably use the isocyanurate trimer of hexamethylene diisocyanate.

Typically require catalytic crosslinking reaction.Preferably by organic tin salt for the purpose.For the purpose of the present invention, particularly preferably make With dibutyl tin laurate (DBTL), because its longer chain acidic group gives its compatibility extra high with base material and composes subsequently Give it and the extra high compatibility of film matrix.

Topcoat material comprises at least one conventional and known imparting color further and/or gives the pigment of effect.Can With select pigment be essentially those of skill in the art be also used for automotive OEM cover with paint, lacquer, colour wash, etc. those.

The example of such pigment is inorganic pigment, such as titanium dioxide, ferrum oxide and carbon black, or common metal pigment (example It is commercially available aluminium bronze, rustless steel bronze) and nonmetal effect pigment (example is pearlescent pigment and coated interference pigment).Can also make Pigment is given, such as AZOpigments and phthalocyanine color by organic group color.

The solvent that can use is those of all the most just solvent bottom paint surfacer explanations of the present invention above.

Applying of priming paint surfacer and finish paint

A kind of curing component, a kind of priming paint surfacer component and a kind of dilution it was usually present before applying priming paint surfacer Agent component.Here curing component comprises cross-linking agent, and priming paint surfacer component comprises base material and the most corresponding pigment and fills out Expect, and thinner composition comprises corresponding solvent.Additive of the present invention can be in priming paint surfacer component or in dilution In agent.Before being close to apply, these three component is mutually mixed with ratio known to the skilled artisan and applies at the bottom of gained Paint surfacer.Any conventional application method can be used in principle, as sprayed, scratch, brush, coming down in torrents, dip-coating, impregnate, drip drench Or roller coat applies.Preferably spray application.During this applies, base material to be applied itself can be static, and applicator device or be System is mobile.Spray application method is preferably used, such as compressed air spraying (pneumatic apply), without air-atomizing, high speed rotating, electrostatic Spray application (ESTA), individually or applies hot-air spraying such as and combines with thermal spray.

The solvent bottom paint surfacer of the present invention applies with conventional and known thickness, such as with 70-170 micron, preferably The wet-film thickness of 90-150 micron.Gained build for example, 50-80 micron the most after solidification, preferably 60-70 micron.

The priming paint surfacer thin film applied applies finish paint thin film.Priming paint surfacer thin film is preferably before applying finish paint It is dried.This such as can be carried out 5-90 minute under room temperature (18-23 DEG C), preferably 20-80 minute, selects very much 30-70 minute.

Apply the universal method of finish paint corresponding to previously above to that described in the solvent bottom paint surfacer of the present invention A bit.

Topcoat material applies with conventional and known thickness, such as with 50-200 micron, and the wet film of preferably 60-150 micron Thickness.Gained build for example, 30-90 micron the most after solidification, preferably 40-70 micron.

The solidification of priming paint surfacer and finish paint is combined and is carried out.This combination curing does not has characteristic for method, but according to often Rule and known method are carried out as heated in forced air oven.Therefore, solidification such as can in room temperature (18-23 DEG C) or For example, 40-100 DEG C, carry out at a temperature of the rising of preferably 50-90 DEG C.Solidification such as can be at 5-120 minute, preferably 10-40 Minute time in carry out.Rapid evaporation stage or preparation drying stage can be optionally present, the most at room temperature before solidification Continue 1-60 minute.

The multicoat paint systems using the solvent bottom paint surfacer of the present invention to produce is characterised by priming paint surfacer Between coating and finish paint and also excellent between priming paint surfacer and base material attachment.If the base material of coating is exposed through the most In atmospheric aging, then equally exist attachment and improve.The improvement of attachment refers to relative to priming paint two road without additive of the present invention The improvement of slurry.

The priming paint surfacer of the present invention is particluarly suitable in the covering with paint of light economic serviceable vehicle application.

In the inventive method also, it is preferred that in embodiment,

I. before applying priming paint surfacer in step (A), priming paint it is applied on base material and is dried gained primer film,

Ii. combination curing is dried primer film and the priming paint surfacer thin film obtained in step (A),

Iii. another coating material in step (B) is base coating material, and the priming paint surfacer being applied to solidification is thin On film and be subsequently dried, and

Iv. clear dope is applied on dry bottom coating film and bottom coating film that combination curing is dried and gained Clear dope thin film.

Term " is dried " and the implication of " solidification " is having already explained above.

Present invention is equally related to the multicoat paint systems that can produce according to this preferred embodiment of the inventive method. All specific spies that this preferred embodiment of solvent bottom paint surfacer of the present invention and also the inventive method is discussed Levying same is preferred to multicoat paint systems.

The base material that can use is identical with described above those.Same particularly preferably aluminum or steel substrate.

Base material can use with untreated form.Or they can wear away in advance.Particularly in automobile recoats, permissible Old impaired finishing agent is removed from base material by sand milling.But, finishing agent that the most only part sand milling is old and not exclusively remove.

Priming paint

Priming paint used is generally made up of bicomponent material, and the latter comprises low viscosity epoxy resin and the polyamine as cross-linking agent Adduct.Primary amine and secondary amine the most at room temperature react with epoxide group, produce secondary amine and tertiary amine respectively.

Generally use aromatic epoxy resin.They are preferably prepared by bisphenol-A and chloropropylene oxide.Preferably prepare by 1 equivalent bisphenol-A The respective rings epoxy resins obtained with 2 equivalent scale chlorohydrin reactions.The aromatic epoxy resin of higher molecular weight is additionally preferably used.These Resin is mainly by making bisphenol A diglycidyl ether prepare with different amounts of bisphenol-a reaction.

Amine used can be ethylenediamine, propane diamine, diethylenetriamines, dipropylenetriamine, isophorone diamine and two (4-amino-3-methylcyclohexyl) methane.Enough number free amine groups are still contained to hand over additionally, can also be produced by polyamine The oligomerization product of connection.Such amine adduct is generally made up of epoxy resin, and the latter reacts with excess polyamine；Such as 2 equivalents two are sub- Ethyl triamine and the adduct of 1 equivalent bisphenol A diglycidyl ether.Another kind of cross-linking agent be have free-end and pendant uncle or The low molecular polyamides of secondary amino group.Polyamide is prepared by making above-mentioned amine and the polymerized fatty acid reaction of excess.

Suitably solvent is esters, alcohols and aromatic compounds.Priming paint used is preferably without chromate.It is anti-that they comprise Rotten pigment is preferably zinc phosphate.Additionally, they comprise titanium dioxide and filler.Additionally, priming paint used can use carbon black and/or ferrum Oxide coloring.

Base coating material

It is possible not only to use Solvent borne base coats material, and aqueous basecoat layer material can be used.

Solvent borne base coats material preferably comprises acetobutyrate and also polyester resin and/or polyacrylate With polymethacrylate resin (the most poly-(methyl) acrylate).Polyester resin and/or poly-(methyl) propylene Acid ester resin preferably further comprises the different functional groups for chemical crosslinking, preferably hydroxyl.

Cross-linking agent used is low viscous aliphatic polyisocyanate adduct, and the latter is with regard to solvent bottom paint two of the present invention The description of road slurry is discussed.Where like the isocyanuric acid ester three very particularly preferably using hexamethylene diisocyanate Aggressiveness.

The solvent that can use is all having been described above with regard to those described in solvent bottom paint surfacer of the present invention.

Aqueous basecoat layer material is preferably used." aqueous " is the term known to those of skill in the art, specifically for not only Comprise organic solvent as solvent, but also based on water as the coating material of solvent." aqueous " is outstanding in the context of the present invention It refers to base coating material preferably containing at least 20 weight %, and more preferably at least 25 weight % water, in each case based on water The total amount of property base coating material." aqueous " is particularly preferably understood to mean except described condition is " based on aqueous basecoat layer material Total amount is the water of at least 20 weight % (or at least 25 weight %) " outward, meet organic solvent ratio in base coating material and exist In the case of every kind, total amount based on aqueous basecoat layer material is less than other prerequisite of 10 weight %.

Additionally, in addition to water, this aqueous basecoat layer material can also comprise organic solvent.Water miscibility is preferably used organic Solvent.

As the base material in aqueous basecoat layer material, optimization polyurethane resin, polyester resin and/or epoxy resin.Equally Likely use poly-(methyl) acrylate.Described organic polymer preferably further comprises for chemical crosslinking not Same functional group, preferably hydroxyl.Organic polymer dispersibility in water can be real via the measure known to those of skill in the art Existing.These potentially include by introduce containing the monomer of such as carboxylate group or sulfonate group organic polymer carried out from Son is modified.Cross-linking agent used is preferably polyisocyanates.Preferably polyisocyanates is all at description solvent bottom paint Those disclosed in during surfacer.

Additionally, Solvent borne base coats material and aqueous basecoat layer material all comprise at least one conventional and known imparting face Color and/or the pigment of imparting effect.The example of such pigment is inorganic pigment, such as titanium dioxide, ferrum oxide and carbon black or conventional (example is pearlescent pigment and interference for metallic pigments (example is commercially available aluminium bronze, rustless steel bronze) and nonmetal effect pigment Pigment).Organic group color can also be used to give pigment, such as AZOpigments and phthalocyanine color.The pigment type of stand-by pigment and The selecting of amount is made in the way of known to those of skill in the art and by required by coating or desired properties controls.For relevant this Further details, see-Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, page 1998,451.

Clear dope

Clear dope is to have protectiveness and/or ornamental performance applying and solidify to be formed afterwards as is known The coating of clear coat.Protectiveness performance for example, resistance to marring and weatherability, especially uv-resistance.Dicoration Can for example, good gloss degree.The clear dope that is commonly used in refinishing field of clear dope used, its select and use right Those of skill in the art are known.This kind of clear dope generally comprises OH official can poly-(methyl) acrylate.As crosslinking Agent uses low viscosity aliphatic polyisocyanate adduct.Can use thus describe the present invention priming paint surfacer time Identical polyisocyanates through using.

Applying of priming paint, priming paint surfacer, priming coat and clear dope

Priming paint such as according to conventional application method, as sprayed, scratch, brush, coming down in torrents, dip-coating, impregnate, drip drench or roller coat execute It is coated with.Preferably spray application.Priming paint applies with conventional and known thickness, such as with 20-70 micron, and preferably 30-50 micron wet Film thickness.Gained build for example, 10-30 micron the most after solidification, preferably 15-20 micron.Applying the present invention's Primer film it is dried before priming paint surfacer.This such as can be carried out 5-90 minute under room temperature (18-23 DEG C), preferably 20-80 Minute, highly preferred 30-70 minute.

A kind of curing component, a kind of priming paint surfacer component and a kind of dilution it was usually present before applying priming paint surfacer Agent component.Now curing component comprises cross-linking agent, and priming paint surfacer component comprises base material and the most corresponding pigment and filler, And thinner composition comprises corresponding solvent.Additive of the present invention can be in priming paint surfacer component or at diluent In.Before being close to apply, these three component is mutually mixed and applies gained priming paint with the ratio known to those of skill in the art Surfacer.The all above-mentioned method of application priming paint described can be used in principle.Preferably spray application.The present invention's is molten Dosage form priming paint surfacer applies with conventional and known thickness, such as with 70-160 micron, and the wet coating thickness of preferably 80-140 micron Degree.Gained build for example, 40-80 micron the most after solidification, preferably 50-70 micron.

Then combination curing primer film and priming paint surfacer thin film.Solidification does not has characteristic for method, but according to often Rule and known method are carried out as heated in forced air oven.Therefore, solidification is such as in room temperature (18-23 DEG C) or such as For 40-100 DEG C, carry out at a temperature of the rising of preferably 50-90 DEG C.Solidification such as can be at 5-120 minute, preferably 10-40 minute Time in carry out.Rapid evaporation stage or preparation drying stage can also be optionally present before solidification, the most at room temperature hold Continuous 1-60 minute.

Base coating material is applied after this.The universal method applying base coating material does not has characteristic and correspondence for method In previous above to those described in priming paint and solvent bottom paint surfacer.

Base coating material applies with conventional and known thickness, such as with 20-100 micron, and the wet film of preferably 30-60 micron Thickness.Gained build for example, 10-40 micron the most after solidification, preferably 14-20 micron.

Drying bottom coating thin film before applying clear dope.This is dried and such as can carry out under room temperature (18-23 DEG C) 5-60 minute, preferably 5-40 minute, highly preferred 10-30 minute.

Clear dope is applied after this.The universal method applying clear dope does not has characteristic and corresponding to early for method First above to described in priming paint and solvent bottom paint surfacer those.Preferably spray application.

Clear dope applies with conventional and known thickness, such as with 50-200 micron, and the wet film of preferably 60-150 micron Thickness.Gained build for example, 25-90 micron the most after solidification, preferably 35-70 micron.

Then combination curing bottom coating film and clear dope thin film.Solidification does not has characteristic for method, but according to often Rule and known method are carried out as heated in forced air oven.Therefore, solidification is such as in room temperature (18-23 DEG C) or such as For 40-100 DEG C, carry out at a temperature of the rising of preferably 50-90 DEG C.Solidification such as can be at 5-120 minute, preferably 10-40 minute Time in carry out.Rapid evaporation stage or preparation drying stage can also be optionally present before solidification, the most at room temperature hold Continuous 1-60 minute.

The multicoat paint systems using solvent bottom paint surfacer of the present invention to produce is characterised by that priming paint surfacer is coated with Between layer and primer coating and also excellent adhesion between priming paint surfacer and priming coat.If coated substrate is such as exposed to Weathering aging, then equally exist attachment and improve.Attachment improvement refers to relative to the priming paint surfacer without additive of the present invention Improve.

The priming paint surfacer of the present invention is especially suitable for automobile recoating.

Additive of the present invention is as the purposes of adhesion promoter

Finally, the invention still further relates at least one additive purposes in solvent bottom paint surfacer, wherein this interpolation Agent can be prepared by making following component reaction:

The alkoxy silane of (b) at least one structure formula (II):

A-R-Si(R’)_x(OR”)_3-x

Wherein

A is OH reactive functional group,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2,

The described present invention is used by special characteristic described in solvent bottom paint surfacer of the present invention equally above all Way is preferred.

Attachment improves the attachment referred to compared with the priming paint surfacer without additive of the present invention and improves.

Attachment such as can be adhered to test by the cross-hatching according to DIN EN ISO 2409 (date: in April, 2010) and be ground Study carefully.Additive of the present invention additionally aids and improves attachment after base material has been subjected to weathering aging.This weathering aging is the most permissible By the controlled condition test simulation according to DIN EN ISO 6270-2CH (date: in JIUYUE, 2005).Additive of the present invention is excellent It is selected to for the covering with paint of light economic serviceable vehicle improve attachment.The most not only improve between base material and priming paint surfacer Attachment, and improve the attachment between priming paint surfacer and finish paint.

Additive of the present invention is also, it is preferred that improve attachment with regard to automobile for recoating.Term " automobile recoating " refers in particular to It is such as to repair the recoating that impaired existing paint finish is carried out in workshop.Defect in coating is likely to directly exist in principle Occur after carrying out OEM covering with paint.Now, term used is OEM recoating.The priming paint surfacer of the present invention can be equally used for OEM In recoating.In both cases, the priming paint surfacer of the present invention also is adapted for repairing the little defect being referred to as " speckle ".This generic operation Also referred to as " speckle repairing ".

Embodiment

Preparation embodiment

Embodiment A: the preparation of α, ω-hydroxy-functional oligoester

Make that reactant shown in table 1 is as described below to react with molar ratio shown in it.First by maleic anhydride (MAn), Adipic acid (AD) and 1,6-HD (HD) add in the 4 liters of stainless steel reactor being equipped with post, condenser and water knockout drum.So Rear addition 3% dimethylbenzene is as entrainer and 0.1% methylnaphthohydroquinone (percentage numeral consumption based on MAn, AD and HD).Gained is anti- Answer mixture lean heated under air 5 hours.Within the whole response time, the temperature of reactant mixture is less than 230 DEG C.Work as acid When value reaches 2mg KOH/g, reactant mixture is cooled to 80 DEG C.The sign data of gained α, ω-hydroxy-functional oligoester As follows:

OH value: 65mg KOH/g

Number-average molecular weight: 1412g/mol

Weight average molecular weight: 3313g/mol

Theoretical carbon-to-carbon double bond content: 1.86mmol/g

Table 1: the amount of the material of reactant used, mol

Embodiment B: prepare additive of the present invention (A1)

27.4 parts are added from ABCR GmbH&Co.KG in the steel reactor being equipped with reflux condenser and thermometer The 3-NCO propyl-triethoxysilicane of (the European retail trader of Gelest INC. product), 9.4 parts of butyl acetates, 0.2 Part 1,4-diazabicyclo [2.2.2] octane and 2.2 parts of triethyl orthoformates.Then by Dropping funnel in nitrogen atmosphere and stirring 46.3 parts of α of lower dropping, ω-hydroxy-functional oligoester (embodiment A) and the mixture of 14.5 parts of butyl acetates.At 70-80 DEG C After lower stirring 6 hours, determined nco value according to DIN EN ISO 11909 (date: in May, 2007) by titrimetry and to continue this anti- Should be 0 until recording nco value.The non-volatile content that additive A 1 of the present invention has is 71.8 weight %.

I) recoat on light economic serviceable vehicle

I.1) preparation comprises the solvent bottom paint surfacer of additive (A1)

Use commercially available priming paint surfacer.It is made up of three kinds of component priming paint surfacer components, firming agent and diluent.This The corresponding composition of a little components is reproduced in table 2.Priming paint surfacer, firming agent and thinner composition are with the ratio of 100:19.5:16 Use, this ratio weight based on each component.This obtains the total amount of priming paint surfacer.Use in each case based on priming paint two The additive of the present invention (A1) that total amount is 0,2,4 and 6 weight % of road slurry.Laboratory stirrer (260-1820rpm) is used for mixing Close.Additive A 1 is added in curing component.

Table 2: the composition of priming paint surfacer used (priming paint surfacer component, firming agent, diluent)

Silquest A-187: γ-glycidoxypropyl trimethoxy silane, Baysilon OL 44: surface is added Agent, activator: the DBTL solution (1 weight %DBTL) in dimethylbenzene/butyl acetate, Nuosperse FA 601: moistening and Dispersant, Aerosil 380: hydrophilic fumed silica, Bentone 34: rheologic additive, Russ flamm 101: carbon Mineral black, Bayferrox 920: yellow ferrum pigment, Incomp KL 30: based on Talcum and the mineral of dolomite, Heucophos ZP0: anti-corrosion paint, Luzenac 10MO: magnesium silicate, Shieldex AC 3: anti-corrosion paint.

I.2) production of coated substrate

Base material used is aluminium sheet, each test board form in a size of 20 × 10 × 0.45cm.First each plate is worn away. This uses P240 level sand paper to carry out.By priming paint surfacer component, firming agent and diluent before being close to apply priming paint surfacer It is used together wood shovel uniform stirring.Apply and carried out by pneumatic spraying.The most at room temperature gained priming paint surfacer thin film is done Dry 60 minutes.Then by the commercially available topcoat material of pneumatic spray application.Then it is dried at room temperature for 10 minutes, is forcing sky subsequently By priming paint surfacer thin film and finish paint thin film combination curing 30 minutes under the base material temperature of 60 DEG C in steam stove.At gained base material In, the build that the build that priming paint surfacer coating has is 77 microns and finish paint has is 75 microns.

Commercially available topcoat material is made up of three kinds of component finish paint components, firming agent and diluent.Finish paint, firming agent and dilution Agent component uses with the ratio of 100:19.5:16, this ratio weight based on each component.Prepare these components of topcoat material Corresponding composition is reproduced in table 3.

Table 3: the composition of finish paint used (finish paint component, firming agent, diluent)

Polyester 3.5VOC is commercially available OH functional polyester (dispersion in organic solvent).Acrylique 324New Process BASF is that OH official can OH-acrylate conventional dispersions in organic solvent.Acrylique TSA UNO BASF is similarly OH official can OH-acrylate conventional dispersions in organic solvent." activator " is catalyst.

I.3) research of adhesion property

The adhesion property of produced coating tests (DIN EN by cross-hatching attachment after 4 different aging conditions ISO 2409；Date: in April, 2010) research.For each priming paint surfacer compositions by its additive level (without adding Agent, 2 weight %, 4 weight % and 6 weight %) characterize, production two samples altogether are also individually separated research.By acquired results pair Each priming paint surfacer compositions forms meansigma methods.

Initially aging condition relates to storing 16 hours at 40 DEG C.For 3 other aging conditions, by sample at conditioning chamber (CC) store at 100% humidity and 40 DEG C in 10 days and (test according to the controlled condition of DIN EN ISO 6270-2CH；Date: In JIUYUE, 2005).Then 1 hour, 3 hours and the attachment of 24 hours study samples after taking out in by conditioning chamber.

Acquired results is shown in Table 4.Column "None" therein refers between base material and priming paint surfacer and at priming paint Between surfacer and finish paint, the most delamination occurs.Additionally, column " Ps/Tc " refers to observe between priming paint surfacer and finish paint Leafing.

The score-system evaluation attachment that scoring is 0-5, scoring 0 imparting is used not to show visible marks after attachment test Coating (extraordinary attachment).Scoring 5 imparting is significantly separated the coating in district after attachment test, and (insufficient is attached ).

Found out can be realized being obviously improved in attachment by using this additive by result shown in table 4.

Table 4: non-doping and the adhesion property of the priming paint surfacer added with additive

Aging condition	Additive-free	2 weight % additives	4 weight % additives	6 weight % additives
					After 40 DEG C 16 hours	1	1	1	0
Leafing:	Nothing	Nothing	Nothing	Nothing
					After CC 1 hour	3	3	0	1
Leafing:	Ps/Tc	Ps/Tc	Nothing	Nothing
					After CC 3 hours	5	5	2	3
Leafing:	Ps/Tc	Ps/Tc	Ps/Tc	Ps/Tc
					After CC 24 hours	4	3	1	2
Leafing:	Ps/Tc	Ps/Tc	Ps/Tc	Ps/Tc

II) automobile recoating

II.1) preparation comprises the solvent bottom paint surfacer of additive (A1)

Use commercially available priming paint surfacer.It is made up of three kinds of component priming paint surfacer components, firming agent and diluent.This The corresponding composition of a little components is reproduced in table 5.Priming paint surfacer component, firming agent and thinner composition are with 100:17.5:13.5 Ratio use, this ratio weight based on each component.This obtains the total amount of priming paint surfacer.Use in each case based on The total amount of priming paint surfacer is the difunctional additive of the present invention (A1) of 0,2,4 and 6 weight %.Use laboratory stirrer (260-1820rpm) agent charging it is added.Additive A 1 is added in curing component.

Table 5: the composition of priming paint surfacer used (priming paint surfacer component, firming agent, diluent)

Polyester 5085 is commercially available OH functional polyester (dispersion in organic solvent).Acrylester365 is OH official's energy OH-acrylate conventional dispersions in organic solvent.

II.2) production of coated substrate

Base material used is steel plate, each test board form in a size of 20 × 10 × 0.3cm.First each plate is worn away. This uses P180 level sand paper to carry out.By priming paint surfacer, firming agent and thinner composition before being close to apply priming paint surfacer It is used together wood shovel uniform stirring.First apply commercially available priming paint, be then dried at room temperature for 10 minutes.Then by pneumatic spraying Apply priming paint surfacer, be dried at room temperature for 10 minutes subsequently.Then by both thin film in forced air oven in 60 DEG C Toast 25 minutes under base material temperature.Priming paint has a build of 16 microns and priming paint surfacer coating has the dried film thickness of micron Degree.The most manual sand milling (P400 sand milling pad) priming paint surfacer also removes sand milling residue by conventional dilution cleaning agent subsequently. Next apply commercially available base coating material, be then dried at room temperature for 10 minutes.Then by commercially available pair of group of pneumatic spray application Divide clear dope, be the most again dried at room temperature for 10 minutes.Then whole base coat-clear coat system is being forced air Stove toasts 10 minutes under the base material temperature of 60 DEG C.Priming coat there is the build of 15 microns and clear coat to have 38 micro- The build of rice.

Use commercially available priming paint.It is made up of three kinds of component abrasives, firming agent and diluent.The respective sets of these components Become to reproduce as follows.Abrasive, firming agent and thinner composition use with the ratio of 100:35.8:8, and this ratio is based on each component Weight.

Table 6: the composition of priming paint used (abrasive component, firming agent, diluent)

Plastopal H 73IB/X 35:1 is urea-formaldehyde resins.Tiona 95 is rutile.Phenodur PR 263 70% is the phenolic resin from Cytec.

Use commercially available base coating material.It is made up of two kinds of component mixing varnish and standardization additive.These components Corresponding composition reproduce as follows.Base coating material uses mixing varnish and standardization additive component to prepare with the ratio of 2:1, should Ratio volume based on each component.

Table 7: the composition of base coating material used

Lanco Pew 1555 is the water-reducible polyethers wax from Lubrizol.

Use commercial clear coating.It is made up of 3 kinds of component abrasives, firming agent and diluent.The phase of these components Reproduction should be formed as follows.Abrasive, firming agent and thinner composition use with the ratio of 100:50:8.6, and this ratio is based on each group The weight divided.

Table 8: the composition of clear dope used (abrasive component, firming agent, diluent)

II.3) research of adhesion property

The adhesion property of produced coating is I.3) under as described under 4 different aging conditions after by cross-hatching adhere to Test (DIN EN ISO 2409；Date: in April, 2010) research.

Acquired results is shown in Table 9.Here column "None" refers to that the most delamination occurs.Additionally, column " Bc/Ps/Tc " refers to not only but also observe layer between priming paint surfacer and priming paint between priming coat and priming paint surfacer From.Column " Bc/Ps/Su " refers to not only between priming coat and priming paint surfacer but also in priming paint surfacer, priming paint and primary coat Leafing is observed between Ceng.Finally, column " Ps/Pr " refers to that only delamination occurs between priming paint surfacer and priming paint.

Table 9: non-doping and the adhesion property of the priming paint surfacer added with additive

Aging condition	Additive-free	2 weight % additives	4 weight % additives	6 weight % additives
					After 40 DEG C 16 hours	4.5	2.5	1.5	0.5
Leafing:	Bc/Ps/Pr	Bc/Ps/Su	Bc/Ps/Pr	Bc/Ps/Su
					After CC 1 hour	1.5	0.5	2.5	3
Leafing:	Bc/Ps/Pr	Bc/Ps/Pr	Bc/Ps/Pr	Bc/Ps/Pr
					After CC 3 hours	2.5	0	1	0
Leafing:	Bc/Ps/Pr	Nothing	Bc/Ps/Pr	Nothing
					After CC 24 hours	1	1	0.5	0.5
Leafing:	Ps/Pr	Bc/Ps/Pr	Bc/Ps/Pr	Nothing

Found out can be realized being obviously improved in attachment by using this additive by result shown in table 9.

Claims

1. a solvent bottom paint surfacer, comprises at least one additive can prepared by making following component reaction:

A () at least one OH value is 30-160mg KOH/g, theoretical carbon-to-carbon double bond content is 1-2.5mmol/g, number-average molecular weight For 1000-3000g/mol and α, ω that weight average molecular weight is 2800-10 000g/mol-hydroxy-functional oligoester, and

The alkoxy silane of (b) at least one structure formula (II):

A-R-Si(R’)_x(OR”)_3-x

Wherein

A is OH reactive functional group,

R be have 2-12 carbon atom aliphatic group, there is the alicyclic group of 3-12 carbon atom, to have 6-12 carbon former The aromatic group of son or there is the araliphatic groups of 7-18 carbon atom,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2,

Condition is α, in all OH groups of ω-hydroxy-functional oligoester at least 90mol% with OH reactive functional group Group's A reaction,

And the weight percent ratio sum of the most all additives of the present invention is based on described solvent bottom paint surfacer total Amount is 0.5-10 weight %.

Solvent bottom paint surfacer the most as claimed in claim 1, wherein said α, ω-hydroxy-functional oligoester makes With at least one saturated linear aliphatic dicarboxylic acid or its anhydride, at least one single unsaturated linear aliphatic dicarboxylic acids or its anhydride and Prepared by least one radical of saturated aliphatic glycol.

3. solvent bottom paint surfacer as required for protection in claim 1 or 2, the percetage by weight ratio of the most all additives Example sum total amount based on described solvent bottom paint surfacer is 1.5-7.5 weight %.

4. solvent bottom paint surfacer required for protection, wherein said α, ω-hydroxyl-functional as any one of claim 1-3 Change oligoester and there is having structure formula (I):

Wherein

Group R₁It is independently selected from linear or cyclic alkylidene,

Group R₂Be independently selected from alkylidene or alkylene group, the ratio of the most specifically chosen alkylidene and alkylene group with The α of structure formula (I), ω-hydroxy-functional oligoester is made to have the theoretical carbon-to-carbon double bond content of 1-2.5mmol/g,

Select exponent m so that the number-average molecular weight of the α of structure formula (I), ω-hydroxy-functional oligoester is 1000-3000g/ mol。

5. solvent bottom paint surfacer as required for protection in claim 4, wherein group R₁Selected from having 6-10 carbon atom Linear alkylene.

6. solvent bottom paint surfacer as required for protection in claim 4 or 5, wherein group R₂Selected from having 4-8 carbon atom Linear alkylene or there is the linear alkylene group of 2-4 carbon atom.

7. solvent bottom paint surfacer required for protection as any one of claim 4-6, wherein said alkoxy silane has There is a general structural Formula (II.1):

OCN-R₁-Si(R’)_x(OR”)_3-x

Wherein

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2.

8. solvent bottom paint surfacer as required for protection in claim 7, wherein R₁For C₂-C₆Alkylidene.

9. solvent bottom paint surfacer as required for protection in claim 7, wherein x=0.

10. the method producing multicoat paint systems on base material, including:

(A) priming paint surfacer required for protection as any one of claim 1-9 is applied,

(B) another coating material is applied.

11. methods as claimed in claim 10, wherein

I. the priming paint surfacer thin film obtained in step (A) it is dried,

Ii. the coating material in step (B) is topcoat material, and

12. 1 kinds of multicoat paint systems that can be produced by method as claimed in claim 11.

13. methods as claimed in claim 10, wherein

Iii. another coating material in step (B) is base coating material, is applied on the priming paint surfacer thin film of solidification And be subsequently dried, and

Iv. clear dope is applied on dry bottom coating film and bottom coating film and gained that combination curing is dried are transparent Paint film.

14. 1 kinds of multicoat paint systems that can be produced by method as claimed in claim 13.

15. at least one additive purposes in solvent bottom paint surfacer, wherein said additive can be as follows by making Component reaction and prepare:

The alkoxy silane of (b) at least one structure formula (II):

A-R-Si(R’)_x(OR”)_3-x

Wherein

A is OH reactive functional group,

Group R ' is selected from C₁-C₁₂Alkyl,

R " it is methyl or ethyl, and

X is 0-2,